CN115988974A - 由陶瓷制成的物品 - Google Patents
由陶瓷制成的物品 Download PDFInfo
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- CN115988974A CN115988974A CN202180053191.6A CN202180053191A CN115988974A CN 115988974 A CN115988974 A CN 115988974A CN 202180053191 A CN202180053191 A CN 202180053191A CN 115988974 A CN115988974 A CN 115988974A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 150000004767 nitrides Chemical class 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910010293 ceramic material Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 4
- 229910006249 ZrSi Inorganic materials 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 12
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 8
- 238000002490 spark plasma sintering Methods 0.000 description 8
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 8
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910021355 zirconium silicide Inorganic materials 0.000 description 7
- 238000009770 conventional sintering Methods 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
本发明涉及一种由包含多种陶瓷相的材料制成的物品，所述材料包括：‑多数陶瓷相，所述多数陶瓷相包含选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和/或碳氮化物，并且重量百分比介于60％与98％之间，‑单一的少数陶瓷相，所述少数陶瓷相由锆和/或铝的硅化物形成，并且总体的重量百分比介于2％与40％之间。本发明还涉及所述物品的制造方法。
Description
技术领域
本发明涉及一种物品，特别是涉及制表业中的外部部件或机芯部件，其由仅包含陶瓷相的复合材料制成。本发明还涉及该物品的制造方法。
背景技术
许多外部部件由复合陶瓷材料制成，其优点尤其是具有非常高的硬度，这保证了它们不被划伤的能力。该表述主要指的是主要由添加了碳化物的氧化物如氧化铝组成的复合材料。例如，它可以由以下复合材料组成：该复合材料包含按重量计70％的Al2O3和用作增强材料的30％的TiC。与诸如不锈钢或陶瓷金属之类的其他材料相比，这些复合材料具有金属光泽很少或没有金属光泽的特点，这对于需要这种光泽的装饰物品来说可能是一个缺点。
基于氮化钛或碳氮化物的材料也是已知的。这些材料由于与其低扩散系数相关联的非常高的熔点(例如对于TiN为2,930℃)而极难致密化。因此，有必要借助快速烧结法，也称为闪蒸，例如SPS烧结(火花等离子体烧结)或压力烧结法(烧结-HIP)或烧结后在极高压力和高温下的固结法，例如HIP(热等静压)。另外，这些烧结工艺不允许获得具有复杂形状的部件。解决此问题的一种方法包括：例如为了制造基于TiN或TiCN的陶瓷金属，添加金属元素作为金属粘合剂。因此，通过添加百分之几的镍或钴，允许在通常在1,500℃范围内的较低温度下进行固结。然而，这些元素具有高致敏性的缺点，因此其应用限于不打算与皮肤接触的物品上。
发明内容
本发明的一个目的是通过提供一种陶瓷材料(也称为复合材料)来克服上述缺点，该陶瓷材料的组成和制造工艺经过优化以满足以下标准：
-避免使用镍或钴之类的致敏元素，
-具有高金属光泽度(65≤L*≤85)，
-能够在大气压、真空或分气压(partial gas pressure)下被致密化，而无需借助高压以便在烧结完成后保持物品坯料的形状，
-对于需要非常好的耐刮擦性的应用，具有至少500HV30、优选至少800HV30和更优选至少1,000HV30的硬度，同时具有足够的韧度，优选Kic高于或等于2.5MPa.m1/2。
为此，本发明提供了一种由包含多种陶瓷相的材料制成的物品，所述材料包括：
-多数(即，占多数的)陶瓷相，其包含来自IVB族(即Ti、Zr和Hf)和/或VB族(即V、Nb和Ta)的一种或多种元素的氮化物和/或碳氮化物，所述多数陶瓷相的重量百分比介于60％与98％之间，
-至少一种少数(即，占少数的)陶瓷相，包括由锆和/或铝的硅化物形成的单一少数陶瓷相，或者包括分别由来自IVB族(Ti、Zr、Hf)、VB族(V、Nb、Ta)和VIB族(Cr、Mo、W)的一种或多种元素的碳化物以及氧化锆和/或氧化铝形成的多个少数陶瓷相，所述至少一种少数陶瓷相整体上的重量百分比介于2％与40％之间。
这样开发的复合材料在抛光后具有与在使用镍或钴作为金属粘合剂的不锈钢或陶瓷金属中观察到的金属光泽度相似的金属光泽度。这些复合材料的另一优点是不含Ni之类的致敏元素。它们还具有高硬度和足够的韧度，可以在非磁性的情况下制造外部部件。此外，它们可以通过传统的粉末冶金工艺(例如压制或注射)或各种专用于制造三维零件的工艺(例如3D打印)来成型，以获得“近净形”零件。具有一定复杂形状的零件可以在介于1,400℃至1,900℃之间的温度下在大气压、真空或分气压下最终固化，即，无需借助显著的压力。
此外，由这种陶瓷材料制成的物品的优点是整体呈现美丽的颜色，色度从黄色到粉红色不等，具体取决于成分。
本发明的其他特征和优点将在以下参考附图作为非限制性示例呈现的优选实施例的描述中显现。
附图说明
图1表示包括由根据本发明的陶瓷材料制成的中间件的钟表。
具体实施方式
本发明涉及一种由仅包含陶瓷相的复合材料制成的物品。该物品可以是装饰物品，例如手表、珠宝、表链等的组成元件，或者更一般地是便携式元件的外部部分，例如手机壳。在制表领域中，该物品可以是外部部件，例如中间件、后盖、表圈、表冠、桥夹板、按钮、表链链节、表盘、指针、表盘刻度等。为了举例，图1中示出了由根据本发明的陶瓷材料制成的中间件。它也可以包括机芯的部件，例如机板或摆陀。
陶瓷材料包括由选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和/或碳氮化物组成的多数相，以及一种或多种少数相。这些少数相可以是锆和/或铝的硅化物，或者选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W的一种或多种元素的碳化物与锆(Zr)和/或铝(Al)的氧化物的组合。优选地，所述多数相由氮化钛和/或碳氮化钛组成。优选地，所述少数相由锆和/或铝的硅化物组成，或者由钨和/或钒的碳化物与锆和/或铝的氧化物的组合组成。
所述多数相的重量百分比介于60％与98％之间，并且所有少数相的重量百分比介于2％至40％之间。优选地，所述多数相的重量百分比介于65％与97％之间，更优选地70％与96％之间，甚至更优选地75％与95％之间。作为多数相的补充，所有少数相的重量百分比优选地介于3％与35％之间，更优选地4％与30％之间，甚至更优选地5％与25％之间。当所述多数相包含选自Ti、Zr、Hf、V、Nb和Ta中的一种或多种元素的氮化物和碳氮化物时，所述氮化物和碳氮化物相对于陶瓷材料的总重量的重量百分比优选地分别介于20％与70％之间，更优选地介于25％与60％之间。当陶瓷材料包括分别为选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W的一种元素或多种元素的碳化物以及氧化物(Al2O3和/或ZrO2)的两种少数相时，它们相对于陶瓷材料的总重量的重量百分比分别优选地介于3％与35％之间，更优选地介于5％与25％之间。
陶瓷制品是通过从粉末混合物开始烧结制成的。制造方法包括以下步骤：
a)可以在潮湿环境中制备具有不同陶瓷粉末的混合物。起始粉末优选地具有小于45μm的d50(中值粒径)。混合可以在研磨机中进行，其在研磨后将粉末颗粒的d50减小到数个微米(<5μm)范围内的尺寸。选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和/或碳氮化物的粉末对于所有这些粉末而言的重量百分比介于60％与98％之间，优选地65％与97％之间，更优选地70％与96％之间，甚至更优选地75％与95％之间。硅化锆和/或硅化铝的粉末或者Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W的碳化物以及锆和/或铝的氧化物的粉末的重量百分比介于2％与40％之间，优选地3％与35％之间，更优选地4％与30％之间，甚至更优选地5％与25％之间。例如，粉末混合物按重量计可以包括以下分布之一，总计100％：
-75％与85％之间的TiN或TiCN和15％与25％之间的ZrSi2，
-85％与95％之间的TiN或TiCN和5％与15％之间的ZrSi2，
-75％与85％之间的TiN或TiCN、5％与15％之间的WC或VC以及5％与15％之间的ZrO2或Al2O3，
-40％与55％之间的TiN、25％与35％之间的TiCN、5％与15％之间的WC或VC以及5％与15％之间的ZrO2。
b)任选地，可以制备包含上述混合物和有机粘合剂体系(石蜡、聚乙烯等)的第二混合物。
c)通过赋予混合物所需物品的形状来形成坯件，例如通过注塑或压制或通过3D打印。
d)在介于1,200℃与2,100℃之间、优选地1,400℃与1,900℃之间的温度下、在分气压、真空或大气压下烧结坯件在10分钟与20小时之间、优选地15分钟与3小时之间的一段时间。如果混合物包含粘合剂体系，则此步骤之前可以是在介于60℃与500℃之间的温度范围内的脱脂步骤。虽然根据本发明的组合物允许在低压下烧结，但本发明不排除通过SPS(火花等离子体烧结)或通过烧结-HIP进行的烧结，之后执行或不执行HIP(热等静压)固结。
将这样获得的坯件冷却并抛光。也可以在抛光前对它进行机加工以获得所需的物品。
由该制造方法得到的物品包括重量百分比与起始粉末的重量百分比接近的多数相和少数相。然而，由于例如烧结过程中的污染或转化，不能排除基础粉末与烧结得到的材料之间的组成和百分比的微小变化。例如，碳化物可以与氮化物反应以形成碳氮化物。
该物品具有CIELAB色彩空间(符合CIE No.15，ISO7724/1，DIN5033Teil7，ASTM E-1164标准)，代表材料反射光的方式的亮度分量L*介于60与85之间，优选地介于65与80之间，更优选地介于70与75之间。有利地，该物品是黄色的，并且具有介于+1与+7之间的a*分量(红色分量)和介于+20与+35之间的b*分量(黄色分量)。有利地，该物品是粉红色的，并且具有介于+2与+15之间的a*分量和介于+2与+10之间的b*分量。
陶瓷材料的HV30硬度高于或等于500，优选地介于800与1,800之间，这取决于成分的类型和百分比。它的韧度Kic高于或等于2，优选地高于或等于2.5MPa.m1/2，其值的范围可高达8MPa.m1/2，根据下式基于硬度试验压痕的对角线四端处的裂纹长度的测量值来确定韧度：
其中P是施加的载荷(N)，a是半对角线(m)，l是测得的裂纹长度(m)。
下文的示例说明了根据本发明的方法和由该方法得到的材料。
在存在溶剂的情况下在研磨机中制备7种粉末混合物。这些混合物是在没有粘合剂的情况下生产的。它们通过压制成型，并在取决于粉末成分的温度下在真空中或在60毫巴的氩或氮的气流中进行烧结。在烧结后，对样品抛光。下面的表1包括成分、烧结参数和机械性能(HV30，K1C)以及实验室比色值。斜体和粗体的值符合硬度高于800维氏硬度、韧度高于2.5MPa.m1/2、L*指数高于70或b*指数高于20的标准，颜色非常黄。
在样品的表面上进行HV30硬度测量，并基于如上所述的硬度测量值来确定韧度。
在以下条件下使用KONICA MINOLTA CM-5分光光度计来测量抛光样品的实验室色度值：SCI(包含镜面反射分量)和SCE(不包含镜面反射分量)测量，倾角为8°，MAV测量区的直径为8mm。
示例1
物品由陶瓷复合材料组成，其中包含氮化钛(TiN)作为多数相，并且包含按重量计最多20％的硅化锆(ZrSi2)作为少数相。根据本发明并且与传统的烧结相比，该复合材料已经通过放电等离子体烧结(SPS)被致密化。测定的硬度为1,328维氏硬度(HV30)，并且韧度为4.3MPa.m1/2。
示例2
物品由陶瓷复合材料组成，其中包含氮化钛(TiN)作为多数相，并且包含按重量计最多10％的硅化锆(ZrSi2)作为少数相。这种90TiN-10ZrSi2复合材料已通过SPS和常规烧结两者被致密化。当通过常规烧结进行烧结时，与SPS烧结相比，观察到硬度下降，从1,302维氏硬度降至863维氏硬度，但保持良好的韧度(4.2对比于4.4MPa.m1/2)。另一方面，通过常规烧结，获得了亮度指数(L*)更高(74.5对比于66.2)的好很多的亮度。常规烧结还允许获得更黄的色调，其中黄色成分b*的值略高。
示例3
物品由陶瓷复合材料组成，其中包含碳氮化钛(TiCN)作为多数相，并且包含按重量计最多10％的硅化锆(ZrSi2)作为少数相。这种90TiCN-10ZrSi2复合材料的维氏硬度较低，为590，但具有最明显的黄色着色，b*值达到27.29。
示例4
物品由陶瓷复合材料组成，其基于氮化钛(TiN)作为多数相，并且碳化钨(WC)和氧化铝(Al2O3)作为少数相，它们按重量计的比例为80TiN-10WC-10Al2O3。这种复合材料在没有压力输入的情况下通过常规烧结被致密化，具有938的维氏硬度、3.6MPam1/2的韧度和强黄色，其中a*值为1.7，b*值为26.2，同时保持美观的金属质感亮度(L*＝72.8)。
示例5
物品由陶瓷复合材料组成，其基于氮化钛(TiN)作为多数相，并且碳化钨(WC)和二氧化锆(ZrO2)作为少数相，它们按重量计的比例为80TiN-10WC-10ZrO2。这种复合材料具有1,187的最大维氏硬度，测定的亮度L*为72.9。这种陶瓷复合材料的颜色为黄色，其中指数a*和b*的值分别为1.48和26.0。因此，用二氧化锆代替氧化铝(示例4)允许将硬度提高249维氏硬度。
示例6
物品由陶瓷复合材料组成，其基于氮化钛(TiN)作为多数相，并且碳化钒(VC)和二氧化锆(ZrO2)作为少数相，它们按重量计的比例为80TiN-10VC-10ZrO2。这种复合材料的维氏硬度为1,275，测定的亮度L*为71.8。这种陶瓷复合材料的颜色为黄色，a*值和b*值分别为2.9和23.4。因此，用碳化钒代替碳化钨(示例5)可以使硬度提高约7％。
示例7
物品由陶瓷复合材料组成，包含氮化钛(TiN)和碳氮化钛(TiCN)作为多数相，并且包含碳化钨(WC)和二氧化锆(ZrO2)作为少数相，它们按重量计的比例为48TiN-32TiCN-10WC-10ZrO2。这种复合材料呈粉红色，其中指数a*和b*的值分别为7.52和8.02。测定的硬度非常高，即1,727维氏硬度，几乎与通过SPS烧结获得的硬度相同。这种提高直接归因于碳化钨的添加。
表1。
Claims (18)
1.一种由包括多种陶瓷相的材料制成的物品，所述材料包括：
-多数陶瓷相，所述多数陶瓷相包含选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和/或碳氮化物，所述多数陶瓷相的重量百分比介于60％与98％之间，
-单一的少数陶瓷相，所述少数陶瓷相由锆和/或铝的硅化物形成，所述少数陶瓷相总体的重量百分比介于2％与40％之间。
2.根据权利要求1所述的物品，其特征在于，所述多数陶瓷相的重量百分比介于65％与97％之间，并且所述少数陶瓷相总体的重量百分比介于3％与35％之间。
3.根据权利要求1或2所述的物品，其特征在于，所述多数陶瓷相的重量百分比介于70％与96％之间，并且所述少数陶瓷相总体的重量百分比介于4％与30％之间。
4.根据前述权利要求中任一项所述的物品，其特征在于，所述多数陶瓷相的重量百分比介于75％与95％之间，并且所述少数陶瓷相总体的重量百分比介于5％与25％之间。
5.根据前述权利要求中任一项所述的物品，其特征在于，当所述多数陶瓷相包含选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和碳氮化物时，所述氮化物和碳氮化物各自相对于陶瓷材料的总重量的重量百分比介于20％与70％之间。
6.根据前一项权利要求所述的物品，其特征在于，所述氮化物和碳氮化物各自相对于陶瓷材料的总重量的重量百分比介于25％与60％之间。
7.根据前述权利要求中任一项所述的物品，其特征在于，所述多数陶瓷相包含氮化钛和/或碳氮化钛。
8.根据前述权利要求中任一项所述的物品，其特征在于，在CIELAB色彩空间中，所述物品的L*分量介于60与85之间，优选地65与80之间。
9.根据前述权利要求中任一项所述的物品，其特征在于，所述物品是黄色的，并且在CIELAB色彩空间中具有介于+1与+7之间的a*分量和介于+20与+35之间的b*分量。
10.根据权利要求1至8中任一项所述的物品，其特征在于，所述物品是粉红色的，并且在CIELAB色彩空间中具有介于+2与+15之间的a*分量和介于+2与+10之间的b*分量。
11.根据前述权利要求中任一项所述的物品，其特征在于，所述物品具有高于或等于500的HV30硬度。
12.根据前述权利要求中任一项所述的物品，其特征在于，所述物品具有介于800与1,800之间的HV30硬度。
13.根据前述权利要求中任一项所述的物品，其特征在于，所述物品具有高于或等于2MPa.m1/2并且优选地高于或等于2.5MPa.m1/2的韧度Kic。
14.根据前述权利要求中任一项所述的物品，其特征在于，所述材料包括总计100％的以下分布中的一者：
-包含75％与85％之间的TiN或TiCN的多数陶瓷相，以及包含15％与25％之间的ZrSi2的少数陶瓷相，
-包含85％与95％之间的TiN或TiCN的多数陶瓷相，以及包含5％与15％之间的ZrSi2的少数陶瓷相。
15.根据前述权利要求中任一项所述的物品，其特征在于，所述物品包括钟表部件。
16.根据前一项权利要求所述的物品，其特征在于，所述物品是选自以下列表的外部部件：中间件、后盖、表圈、按钮、表冠、表链链节、表盘、指针和表盘刻度，或者所述物品是选自以下列表的机芯部件：机板、桥夹板和摆陀。
17.一种制造物品的方法，包括以下相继的步骤：
a)制备混合物，所述混合物包含选自Ti、Zr、Hf、V、Nb和Ta的一种或多种元素的氮化物和/或碳氮化物的粉末，所述氮化物和/或碳氮化物的粉末的重量百分比介于60％与98％之间，并且所述混合物还包含如下所述的至少一种粉末：
-所述至少一种粉末由锆和/或铝的硅化物形成，
-所述至少一种粉末总体的重量百分比介于2％与40％之间，
b)通过赋予所述混合物所述物品的形状来形成坯件，
c)在介于1,200℃与2,100℃之间、优选地介于1,400℃与1,900℃之间的温度下烧结所述坯件一段时间，所述一段时间介于30分钟与20小时之间、优选地介于15分钟与3小时之间。
18.根据权利要求20所述的制造方法，其特征在于，步骤a)的粉末混合物包括总计100％的以下分布中的一者：
-在75％与85％之间的TiN或TiCN，以及在15％与25％之间的ZrSi2，
-在85％与95％之间的TiN或TiCN，以及在5％与15％之间的ZrSi2。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20198345.9 | 2020-09-25 | ||
| EP20198345.9A EP3974405A1 (fr) | 2020-09-25 | 2020-09-25 | Article décoratif en ceramique |
| PCT/EP2021/071130 WO2022063462A1 (fr) | 2020-09-25 | 2021-07-28 | Article en ceramique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115988974A true CN115988974A (zh) | 2023-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180053191.6A Pending CN115988974A (zh) | 2020-09-25 | 2021-07-28 | 由陶瓷制成的物品 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20230295053A1 (zh) |
| EP (2) | EP3974405A1 (zh) |
| JP (1) | JP7557048B2 (zh) |
| CN (1) | CN115988974A (zh) |
| WO (1) | WO2022063462A1 (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4328271A1 (fr) * | 2022-08-23 | 2024-02-28 | The Swatch Group Research and Development Ltd | Article en ceramique de couleur vive et son procede de fabrication |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP7557048B2 (ja) | 2024-09-26 |
| US20230295053A1 (en) | 2023-09-21 |
| EP3974405A1 (fr) | 2022-03-30 |
| EP4217331A1 (fr) | 2023-08-02 |
| WO2022063462A1 (fr) | 2022-03-31 |
| JP2023537425A (ja) | 2023-08-31 |
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